Plasticized cellulose derivative composition



photoslaphic Patented July 15, 1941 ems'rr'orzan oaurmosa DERIVATIVE comosrrron Joseph B. Dickey and James G. McNally, Inches I Batman Kodak ter, N. Y., assign DIM, Jersey No Drawing. Application December 16,

Serial No.z48,202

2 Claims. This invention relates to compositions of mat- I ter in which cellulose derivatives, such as cellulose acetate, cellulose nitrate or cellulose others,

or: Rochester, N. Y., a corporation or New Oomthefincreasing number; of desirable properties required of the cellulose derivative for most purposes has made the discovery of new and ecoare combined or mixed with other substances.

such as a compatible plasticizer, and a common solventior both, with or without other useful addition agents, so that the resulting product will have properties such as will make the com-- position highly advantageous for use in the plastic and analogous arts, such, for instance, the

manufacture of wrapping sheets,'photographic film, artificial silk varnishes or lacquers, and" the like.

One object of this-invention is to produce a composition of matter-which may be made into permanently transparent, trong and flexible sheets or films of desired thinness which are substantiallywaterproof, are unaffected by ordinary fluids and possess the desired properties of a support for sensitive "photographic coatings. Another object of our invention is to produce a composition which is capable of easy I and convenient manipulation in the plastic and analogous arts, such ,as .in the manufacture of sheets, films, artificial silk filaments, varnishes, lacquers and the like, and to produce a composition which will not injure, or be injured by, the substances or surfaces with which it is associated during manufacture. Other objects will be come apparent to those skilled in the art to which this invention pertains.

While cellulose acetates, nitrates and ethers have been known for decades it has also. been.

known that to utilize them in the various plastic arts it is necessary to mix therewith such plasticizing or conditioning agents as camphor, castor oil, triphenyl phosphate, monochlornaphthalene or the like. Certain of these and other addition agents are also added for the purpose of reducing the infiammability of the product. Plastic inducing agents, such as the higher alcohols and their esters, are sometimes also added. Similarly, addition compounds of various kinds have been employed to increase flexibility, transparency, toughness, and other properties which will enhance the value of the resulting product. Addition products for the same or similar purposes are also added to cellulose acetates, nitrates and ethers to prepare them for use in the other plastic arts, such as in the manufacture of lacquers,

varnishes, artificial silk filaments, moulded compounds'and the like. While the plasticizers or other addition agents heretofore discovered have had their utility in the art, the increasing use to which cellulose derivatives have been put and nomical plasticizers or other addition agents a matter of considerable importance to the art.

We have discovered that valuable properties may be induced in and/or contributed to compositions containing cellulose derivatives suchas cellulose acetate, by adding thereto as plasticizing compounds morpholine derivatives having the general formula:

whereinn represents a positive integer greaterthan one and less than 4, It represents a divalent organic group, Z represents a group selected from the group consisting of hydrogen and an organic group of the following general formula:

wherein d represents a positive integer greater than one and less than four.

These compounds may be prepared by treating hydroxyalkylated .morpholine derivatives with the desired acid, acid chloride, or anhydride by known methods. -,In case'an acid is used, the compound may be esterified by removing water by means of an azeotrcpic withdrawing agent.

Examples of the preparation of typical compounds of this type are as follows:

PREPARATION or Es'rsss Morpholine ethyl furoate 143 parts of furoyl chlorideand a solution of parts sodium hydroxide in 225 parts water are added simultaneously to 130 parts morpholine ethanol, with vigorous stirring. The temperature is'kept at 15-20 by means of an ice bath. The

mixture is then stirred two hours, allowing the temperature to rise to that of the room. The

resultant aqueous oil mix is then extracted twice with benzene (200 and parts) The benzene is distilled off at atmospheric pressure and the residue fractionated in vacuo. Morpholineethyl furoate boils at -195/21 mm. It is soluble in water.

\ Morpholine ethyl tetrahildroluroate 223 parts of morpholine mumss parts Raney nickel are shaken in an autoclave Cellulose butyl'ate Propylene chloride 300 Acetone 100 Example 8 1 Parts Cellulose acetate butyrate. 100 B-Hydroxyethyl morpholine lau'rate .15 Triphenyl thiophosphate 8 Ethylene chloride 400 Methanol 100 Esample 9 l Parts Ethyl cellulose 100 hf-It cm-N p I cm. 8 memo-0H; om-ood-mm Acetone 400 Example 7 100 p-Hydroxyethyl morphollne tetrahydroiuroate so produced has permanently brilliant transparj ency and low inflammabillty, burning no more readily than ordinary newsprint. Such film is exceedingly tough and flexible, as shown by the fact that it will'withstand many folds upon a duced from our new composition is considerably with hydrogen at 2000 lb. pressure and 150v C, until the theoretical quantity 0! hydrogen has been absorbed '(4-0 hr.) The resulting product is then filtered and distilled. Morpholine ethyl tetrahydrofuroate,boils at 185-190/23 mm. It is water soluble. v

Morpholine ethyl succinate 118 parts succinic acid, 120 parts morpholine ethanol, 150 parts toluene, and 1 part p-toluene sulionic acid are distilled in such a way that the toluene is continuously separated from the water rormed and returned to the reaction. The heating is discontinued when 18 parts of water have been collected. The solution is then treated with a small amount of sodium bicarbonate, filtered, A and the toluene distilled 01!. The residue is then fractionated in vacuo. The ester boils at 250- 25576 mm. It is water soluble.

In the following examples and description we have set forth several of the preferred embodiments of our invention, but they are included merely for purposes of illustration and not as a limitation thereof:

Example 1 Parts Cellulose acetate 100 p-H'ydroxyethyl morpholine acetate Acetone 400 Example 2 Parts Cellulose acetate -Hydroxypropyl morpholine butyrate 20 Acetone r. 300 Methanol 100 Example 3 Parts Cellulose acetate 100 'p Hydroxyethyl morpholine succinate 30 .Ethylene chloride"; 300 Dioxaneh 100 Example 4 Parts Cellulose acetate; 100 -Hydroxypropyl morpholine adipate 20 Triphenyl phosphate 20 Acetone v 300 Ethyl acetate 100 Example 5 Parts Cellulose acetate propionate 100 Butyl phthalate, 20 fl-Hydroxyethyl morpholine phthalate 30 Propylene chloride 200 Ethyl lactate- 100 Acetone 100 Example 6 Parts Cellulose nitrate '100 ,s-Hydroxyp-ethoxyethyl morpholine furoate 3, Ester g m 40 Ethyl aceta 200 I Toluene 100 Ethanol 100 approximately 30 to 40 parts thereof.

modified Schopper fold-tester (commonly used for such purposes) without breaking and that even after being subjected for a considerable number of days to air maintained at a temperature of 65 C. the film still maintains flexibility (in contrast to almost complete lack of fiexibility where no plasticizer is used) demonstrating that the film will withstand ordinary usage satisfactorily for many years. The sum total ot the above advantageous properties of a product proin excess of that of products produced with what have previously been regarded as the better plasticizers.

In order that those skilled in this art may better understand our invention we would state, by way or illustration, that for the manufacture oi photographic film or other sheets our new composition of matter may be compounded as 101- lows: 100 parts of acetone soluble cellulose acetate, i. e. cellulose acetate containing from 38% to 42% acetyl radical, approximately, is dissolved with stirring at atmospheric temperature in 300 to 500 parts,.preterably 400 parts, by weight, of acetone. To this solution may be added from 5-50 parts by weight, of anyone of the above plasticizers, it being found preferable to employ The amount of plasticizer may be'decreased or increased, depending upon whether it is desired to decrease or increase, respectively the properties which this plasticizer contributes to the finished product. The amount of solvent employed may also be decreased or increased, depending upon whether it is desired to have a more or less i'reel flowing composition, respectively.

Other similar solvents than those mentioned aaaacia above which are compatible with the'cellulose acetate and our new plasticizers may also occur to those skilled in this art. In like manner our plasticizers may be compounded with other single or mixed organic esters of cellulose, such as cellulose aceto-stearate, aceto-malate, or celluuitable solvent which will dissolve both the cellulosic derivative and the plasticizer being'employed. t

Inasmuch as our above described composition 'of matter is quite useful in the production of films and sheets it will be apparent that our new plasticizers may also be employed with advantage in the other branches of the plastic art. For example, as set forth in our copending ap ni cation filed of even date herewith, compositions of matter similar to those described herein may be employed in the manufacture of artificial silk by the dry spinning method. With a proper-coagulating bath they may be employed forwet spinhing. It may be desired to employ a composition of difierent viscosity or evaporation character istics, but this is a mere matter of changing the solvent proportion or adding evaporation retardents or other high or intermediate boiling constituents, as has been well known in the art for more than a decade.

- Our novel plasticizers maybe employed also with advantage in connection with a number of the known lacquer and varnish formulas with which it may be found to be compatible. In such cases the plasticizer is usually first. put into solution with the cellulose derivative solution and, if

' non-solvents are added, only to such an extent as will not precipitate the derivative irom'solution. Also the plasticizer is usually employed in larger amounts, such as from 50 to 60 parts, in cornpounding lacquers. Other uses within the scope of our invention will also suggest themselves to those skilled in the art and are to be included within the scope of the claims appended hereto.

What weclaim is:"

1. A composition of matter comprising .a cellulose derivative selected from the group consisting of cellulose esters and ethers and 15-80% based lose nitro-acetate, or with the cellulose ethers, a

g 3 on the weight of the cellulose derivative of a morpholine ester having the general formula:

wherein n represents a positive, integer greater integer greater ing the general formula:

wherein n represents a positive integer greater than one and less than four, R represents a divalent organic group, 2 represents a group selected from the group consisting of hydrogen and an organic group of the following general formula:

c-o H: H: wherein at represents a positive integer greater than one and less than four.

' JOSEPH B. DICKEY. JAMES G. McNALLY.

group of the following general- 

